A kind of preparation method of 4-cyclopropyl-1-isothiocyanatonaphthalene and intermediate 4-cyclopropyl-1-naphthalene formaldehyde oxime/halide

A technology of isothiocyanate and naphthalene formaldehyde oxime, which is applied in the field of organic chemistry, can solve the problems of high labor protection cost, difficulty in large-scale production, and large environmental impact, so as to reduce labor protection cost, improve safety, and reduce labor environmental impact small effect

Active Publication Date: 2014-10-15
ZHEJIANG HUABANG MEDICAL & CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0018] The present invention aims to solve the above problems and overcome the inherent shortcomings of the traditional method, that is, the "naphthylamine method" is extremely inconvenient to operate, has a large impact on the environment, high labor protection costs, and is not easy to achieve large-scale production.

Method used

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  • A kind of preparation method of 4-cyclopropyl-1-isothiocyanatonaphthalene and intermediate 4-cyclopropyl-1-naphthalene formaldehyde oxime/halide
  • A kind of preparation method of 4-cyclopropyl-1-isothiocyanatonaphthalene and intermediate 4-cyclopropyl-1-naphthalene formaldehyde oxime/halide
  • A kind of preparation method of 4-cyclopropyl-1-isothiocyanatonaphthalene and intermediate 4-cyclopropyl-1-naphthalene formaldehyde oxime/halide

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Experimental program
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Effect test

Embodiment 1

[0040] The synthetic route diagram of the present invention is as follows:

[0041]

[0042] The implementation process of synthetic route of the present invention is briefly described as follows:

[0043] 1. Obtain 4-cyclopropyl-1-naphthaldehyde oxime by reacting 4-cyclopropyl-1-naphthaldehyde with hydroxylamine or hydroxylamine derivatives. The structural formula is as follows:

[0044]

[0045] Add 9.8g (50mmol) of 4-cyclopropyl-1-naphthaldehyde, 5.2g (75mmol, 1.5eq.) of hydroxylamine hydrochloride, and 4.1g (75mmol, 1.5eq.) of anhydrous sodium acetate into 100ml of methanol, stir and reflux for 8 hours, cooled to room temperature, filtered, and the filtrate was dispersed in 200ml of water, filtered, rinsed with water, dried and crystallized with n-hexane to obtain 10.0 g of 4-cyclopropyl-1-naphthaldoxime as a white crystalline solid with a yield of 95%.

[0046] Wherein, the preparation method of the 4-cyclopropyl-1-naphthaldehyde used in step (1):

[0047] Dissol...

Embodiment 2

[0059] Add 9.8g (50mmol) of 4-cyclopropyl-1-naphthalene formaldehyde, 8.2g (50mmol, 2.0eq.) of hydroxylamine sulfate, and 4.1g (75mmol, 1.5eq.) of anhydrous sodium acetate into 100ml of methanol, stir and reflux to react 8 hours, cooled to room temperature, filtered, the filtrate was dispersed in 200ml of water, filtered, rinsed with water, dried and crystallized with n-hexane to obtain 9.6 g of 4-cyclopropyl-1-naphthaldoxime as a white crystalline solid with a yield of 91%.

[0060] Dissolve 9.5g (45mmol) of the obtained intermediate 4-cyclopropyl-1-naphthaldoxime in 100ml of acetonitrile, and add 3.5g (15mmol, 1.0eq.) of trichloroisocyanuric acid in batches. After the addition was complete, the stirring reaction was continued for 2.0 hours. The reaction solution was dispersed into 500ml of water, a large amount of white solid crystals were precipitated, filtered, rinsed with water, sucked dry, and dried in vacuum to obtain 9.1g of 4-cyclopropyl-1-naphthaldoxime chloride with...

Embodiment 3

[0063] Add 9.8g (50mmol) of 4-cyclopropyl-1-naphthaldehyde, 40ml (60mmol, 1.2eq.) of 1.5M hydroxylamine methanol solution, add 100ml methanol, stir and reflux for 1.5 hours, cool to room temperature, and disperse the reaction solution to 200ml of water, filtered, washed with water, dried and crystallized with n-hexane to obtain 10.0 g of white crystalline solid of 4-cyclopropyl-1-naphthalene formaldehyde oxime, yield 95%.

[0064] Dissolve 9.5 g (45 mmol) of the resulting intermediate 4-cyclopropyl-1-naphthalene formaldehyde oxime in 100 ml of acetonitrile, and slowly add 8.9 g of N-bromosuccinimide (50 mmol, 1.0 eq.) in 100 ml of MeCN solution. After the dropwise addition was completed, the mixture was kept warm and stirred for 2.0 hours. The reaction solution was dispersed into 800ml of water, a large amount of white solid crystals were precipitated, filtered, rinsed with water, sucked dry, and dried in vacuum to obtain 12.6g of 4-cyclopropyl-1-naphthaldoxime bromide with a...

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Abstract

The invention provides a preparation method of 4-cyclopropyl-1-naphthaline isothiocyanate, which is characterized in that the 4-cyclopropyl-1-naphthaline isothiocyanate is synthesized by taking 4-cyclopropyl-1-naphthaldehydes as an initial raw material through three-step reaction of oximation, halogenation and vulcanization. Meanwhile, the invention discloses a preparation method of an intermediate 4-cyclopropyl-1-naphthaldehyde oxime / halide of the 4-cyclopropyl-1-naphthaldehydes. When the 4-cyclopropyl-1-naphthaline isothiocyanate is prepared with the method disclosed in the invention, thiophosgene, which has strong toxicity and bad smell, is not needed to be used. The invention has the advantages of convenience in operation, small influence to environment, good safety, good product quality and high yield. Moreover, the separation and purification of a product is easy and is simple to operate.

Description

technical field [0001] The invention relates to a preparation method of 4-cyclopropyl-1-isothiocyanatonaphthalene and an intermediate 4-cyclopropyl-1-naphthalene formaldehyde oxime / halide, belonging to the technical field of organic chemistry. Background technique [0002] The compound involved in the present invention is 4-cyclopropyl-1-isothiocyanatonaphthalene, the compound CAS registration number 878671-95-5 , the specific structural formula is as follows: [0003] [0004] The compound is the raw material of the key intermediate RDEA806-2 (see the structure below) of the new-generation non-nucleoside anti-HIV drug RDEA806 (see the structure below). RDEA806-2 can be easily obtained via 4-cyclopropyl-1-isothiocyanatonaphthalene (refer to US Patent US7435752), and the reaction formula is as follows: [0005] [0006] With regard to 4-cyclopropyl-1-isothiocyanatonaphthalene, only a few patents have publicly reported its synthesis method. [0007] U.S. Patent No. 7,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C331/28C07C251/48
Inventor 洪道送刘新科伍小唐
Owner ZHEJIANG HUABANG MEDICAL & CHEM
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